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OH formation dynamics in 193nm photolysis of 2-methoxyethanol: A laser induced fluorescence study

Authors :
Awadhesh Kumar
Prakash D. Naik
Sumana SenGupta
Hari P. Upadhyaya
Source :
Chemical Physics. 443:8-16
Publication Year :
2014
Publisher :
Elsevier BV, 2014.

Abstract

Dynamics of OH radical formation in the 193 nm photolysis of 2-methoxyethanol is studied using Laser Photolysis–Laser Induced Fluorescence technique. The nascent state distribution of the OH radical is measured. The OH fragments are formed vibrationally cold, characterized by a Boltzmann-like single rotational temperature of 450 ± 100 K. The spin–orbit and Λ -doublet ratios of OH fragments are measured. The relative average translational energy of the OH channel is determined to be 17.0 ± 3.0 kcal/mol. The experimental studies along with theoretical calculations suggest a complex mechanism for OH formation consisting of at least three pathways. The prominent pathway at shorter timescale ( 1 ms) involves a series of reaction with initial H3C–OCH2CH2OH bond cleavage, followed by rearrangement of OCH2CH2OH to CH2OCH2OH, and a final concerted step to generate OH and ethylene epoxide.

Details

ISSN :
03010104
Volume :
443
Database :
OpenAIRE
Journal :
Chemical Physics
Accession number :
edsair.doi...........c0e68d347ceff972f538bdf2a7cb1cd7
Full Text :
https://doi.org/10.1016/j.chemphys.2014.08.005